Effect of Carbon Insertion on the Structural and Magnetic Properties of NdScSi.

The investigation of layered intermetallic compounds containing light elements like hydrogen has great potential for superconductivity. We studied the insertion of carbon atoms in CeScSi-type intermetallics (an ordered variant of the La2Sb structure type), and here, we report the new carbide NdScSiC0.5. Carbon insertion keeps the pristine compound's space group, I4/mmm, but causes an anisotropic expansion of the unit cell with an increase in the a parameter and a decrease of the c parameter. X-ray and neutron diffraction measurements indicate the existence of a NdScSiCx solid solution (0.2 < x ≤ 0.5) with carbon atoms occupying only the Sc4Nd2 octahedral sites while leaving the Nd4 tetrahedral sites vacant. Magnetization measurements unveil a linear reduction of the ferromagnetic ordering temperature from TC = ∼171 K to ∼50 K with increasing carbon content. The ferromagnetic structures of the pristine NdScSi and the filled NdScSiC0.5 have been determined from neutron diffraction measurements. Finally, we discuss the effect of carbon versus hydrogen insertion on electronic and magnetic properties based on density functional theory calculations. Although the unpaired spin density channels between Nd and Sc atoms (responsible of the high Curie temperature in NdScSi) are reduced upon carbon insertion, the strong Nd-C interaction, linked to a reduced c lattice parameter in NdScSiC0.5, ensures a strong magnetic coupling between the Nd double layer along the c axis and the ferromagnetic order is preserved.

The Mg-Rich Phase NdNiMg15: Structural and Magnetic Properties.

The intermetallic NdNiMg15 is the Mg-richest phase (more than 88 atom % of Mg) discovered in the Mg-Nd-Ni system. Its structure was determined by X-ray diffraction on single crystal with the following crystal data: tetragonal system, P4/ nmm, Z = 2, a = 10.0602(1) Å, c = 7.7612(2) Å, dcalc = 2.40 g·cm-3. Its structure is made of a three-dimensional framework of magnesium atoms showing channels filled by one-dimensional chain consisting of alternating Nd and Ni atoms along the c-axis. Anti-ferromagnetic ordering was observed with TN = 9 K, which is remarkably high considering the long distances between magnetic atoms, that is, Nd atoms. The effective magnetic moment µeff is equal to 3.58 µB, which is consistent with magnetic Nd3+ ions and weakly or nonmagnetic Ni atoms. Below TN, the M( H) curves show field-induced metamagnetic transitions at critical fields increasing with decreasing temperatures. The magnetic structure of NdNiMg15 was determined from neutron powder diffraction data by considering the propagation vector k = (1/2 1/2 0). This magnetic structure consists in ferromagnetic chains along the c-axis of Nd atoms carrying moments, only separated by Ni atoms. The chains are ferromagnetically coupled within planes perpendicular to the [110] direction, and these planes are anti-ferromagnetically coupled to neighboring planes forming a checkerboard-like magnetic structure.

Hydrogen Insertion in the Intermetallic GdScGe: A Drastic Reduction of the Dimensionality of the Magnetic and Transport Properties.

Intermetallic phases have been investigated with respect to their ability to accept small atoms in interstitial sites without changing the host structure. Among those, the intermetallic compounds crystallizing in the tetragonal CeScSi-type structure are able to absorb hydrogen atoms. These compounds are of particular interest because they can show electride-like character and, therefore, can be exploited as new catalysts. Here we report the case of GdScGe which uptakes hydrogen at 623 K and under a H2 gas pressure between 0.5 and 4 MPa. The formation of the hydride GdScGeH, with H atoms entering into the [Gd4] tetrahedra, preserves the host structure but induces an anisotropic volume expansion with a strong increase of the c-parameter and a slight decrease of the a-parameter. Interestingly, we show for the first time for this family of materials that hydrogen insertion reduces the dimensionality of the magnetic and transport properties from 3D to quasi-2D which results in a vanishing of the ferromagnetic order ( TC = 350 K for GdScGe) and a change of the metallic conduction behavior to a nonmetallic one. As evidenced by density functional theory calculations, such drastic effects are accounted for through the Gd-H chemical bonding effect and the oxidizing effect of H whereas the volume expansion plays only a minor role.

Stabilization by Si substitution of the pseudobinary compound Gd(2)(Co(3-x)Si(x)) with magnetocaloric properties around room temperature.

We report the discovery of a new solid solution Gd2(Co3-xSix) with 0.29 < x < 0.50 in the Gd-Co-Si ternary system. Members of this solid solution crystallize with the La2Ni3-type structure and correspond to the stabilization of "Gd2Co3" through silicon substitution. The structure of the member Gd2(Co2.53(3)Si0.47) was determined by X-ray diffraction on a single crystal. It crystallizes with the space group Cmce and cell parameters a = 5.3833(4), b = 9.5535(6), and c = 7.1233(5) Å. Co/Si mixing is observed on two crystallographic positions. All compounds studied in the solid solution present a ferrimagnetic order with a strong composition-dependent Curie temperature TC with 280 K < TC < 338 K. The magnetocaloric effect, which amounts to around 1.7 J K(-1) kg(-1) for ΔH = 2 T, is interestingly tunable around room temperature over a temperature span of 60 K through only 4-5% of composition change.

NdNiMg5, a new magnesium-rich phase with an unusual structural type.

The new intermetallic NdNiMg5 was discovered during the study of the Mg-rich part of the Mg-Nd-Ni system. It was synthetized by melting of the constituent elements in a sealed tantalum tube with subsequent annealing. Its structure was determined by X-ray diffraction on a single crystal. Crystal data: orthorhombic system, Cmcm, Z = 4, a = 4.4799(2) Å, b = 9.9827(3) Å, c = 13.7854(10) Å, d(calc) = 3.49 g·cm(-3). Its structure is made of infinite layers of Mg atoms that form blocks stacked along the c axis. These blocks, with a close-packed array of Mg atoms, are separated by infinite NiNd layers and connected through short Mg-Mg bonds. In the NiNd layer, the Ni and Nd atoms form an ordered graphite-type network. Antiferromagnetic ordering is observed with T(N) = 12 K, and the effective magnetic moment µeff is equal to 3.89(1) µB.

Magnetic properties of the RbMnPO4 zeolite-ABW-type material: a frustrated zigzag spin chain.

The crystal structure and magnetic properties of the RbMnPO4 zeolite-ABW-type material have been studied by temperature-dependent neutron powder diffraction, low-temperature magnetometry, and heat capacity measurements. RbMnPO4 represents a rare example of a weak ferromagnetic polar material, containing Mn(2+) ions with TN = 4.7 K. The neutron powder diffraction pattern recorded at T = 10 K shows that the compound crystallizes in the chiral and polar monoclinic space group P2(1) (No. 4) with the unit cell parameters: a = 8.94635(9), b = 5.43415(5), and c = 9.10250(8) Å and ß = 90.4209(6)°. A close inspection of the crystal structure of RbMnPO4 shows that this material presents two different types of zigzag chains running along the b axis. This is a unique feature among the zeolite-ABW-type materials exhibiting the P2(1) symmetry. At low temperature, RbMnPO4 exhibits a canted antiferromagnetic structure characterized by the propagation vector k1 = 0, resulting in the magnetic symmetry P2(1)'. The magnetic moments lie mostly along the b axis with the ferromagnetic component being in the ac plane. Due to the geometrical frustration present in this system, an intermediate phase appears within the temperature range 4.7-5.1 K characterized by the propagation vector k2 = (kx, 0, kz) with kx/kz ≈ 2. This ratio is reminiscent of the multiferroic phase of the orthorhombic RMnO3 phases (R = rare earth), suggesting that RbMnPO4 could present some multiferroic properties at low temperature. Our density functional calculations confirm the presence of magnetic frustration, which explains this intermediate incommensurate phase. Taking into account the strongest magnetic interactions, we are able to reproduce the magnetic structure observed experimentally at low temperature.

Topotactic fluorination of intermetallics as an efficient route towards quantum materials.

Intermetallics represent an important family of compounds, in which insertion of light elements (H, B, C, N) has been widely explored for decades to synthesize novel phases and promote functional materials such as permanent magnets or magnetocalorics. Fluorine insertion, however, has remained elusive so far since the strong reactivity of this atypical element, the most electronegative one, tends to produce the chemical decomposition of these systems. Here, we introduce a topochemical method to intercalate fluorine atoms into intermetallics, using perfluorocarbon reactant with covalent C-F bonds. We demonstrate the potential of this approach with the synthesis of non-stoichiometric mixed anion (Si-F) LaFeSiFx single-crystals, which are further shown to host FeSi-based superconductivity. Fluorine topochemistry on intermetallics is thus proven to be an effective route to provide functional materials where the coexistence of ionic and metallo-covalent blocks, and their interactions through inductive effects, is at the root of their functional properties.

Drastic change of the ferromagnetic properties of the ternary germanide GdTiGe through hydrogen insertion.

Hydrogen absorption of the CeFeSi- and CeScSi-type forms of GdTiGe was performed. Before hydrogenation they show an antiferromagnetic transition at around 412 K and a ferromagnetic transition at 376 K, respectively. Hydrogenation of both forms leads to formation of the same hydride GdTiGeH which crystallizes with a filled CeScSi-type structure where all the [Gd(4)] tetrahedra are filled by hydrogen. This hydride is paramagnetic in the temperature range 4-300 K. The slightly negative value of the paramagnetic Curie temperature θ(p) confirms that all ferromagnetic interactions were destroyed in the case of the CeScSi-type form. From first-principles calculations with the PAW GGA methodology, the localization of hydrogen within the [Gd(4)] tetrahedra was confirmed through energetic stabilization. It was also seen that the energy changes significantly with volume, indicating the itinerant (delocalized) role of the electrons in the magnetism.

Synthesis, characterization, and crystallographic study of the PbO-Bi2O3-V2O5 system: Pb(3-x)Bi(2x/3)V2O8 (0.20 < or = x < or = 0.50).

A new solid solution Pb(3-x)Bi(2x/3)V(2)O(8) (0.20 < or = x < or = 0.50), stabilizing the high-temperature gamma form of Pb(3)V(2)O(8), has been isolated in the system Pb(3)V(2)O(8)-BiVO(4). The single-crystal structure of the composition x = 0.50 (Pb(2.5)Bi(1/3)V(2)O(8)) was solved using single-crystal X-ray diffraction (XRD) technique. The compound crystallizes in the trigonal crystal system R3m (No. 166) with a palmierite structural type with a = 5.7463(3) A, c = 20.3047(12) A, V = 580.64(5) A(3), and Z = 3. The final R1 value of 0.0406 was achieved for 217 independent reflections during the structure refinement. The variable-temperature powder XRD shows the absence of any phase transition for all of the members of the solid solution in the limit of 398-80 K. The new solid solution has been characterized by neutron powder diffraction, solid-state UV-vis diffuse-reflectance spectra, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). Alternating-current impedance studies indicate conductivity on the order of 10(-4) Omega(-1) cm(-1) for Pb(2.5)Bi(1/3)V(2)O(8). The change in color of the samples from brown to yellow at high temperature was explained by XPS studies, which indicate the plausible formation of the ppm level of Bi(2)O(3) at such elevated temperature ranges.

Hydrogenation inducing ferromagnetism in the ternary antiferromagnet NdCoSi.

The hydride NdCoSiH obtained by exposure at 523 K of the ternary antiferromagnet NdCoSi under a pressure of 4 MPa of hydrogen crystallizes in the tetragonal ZrCuSiAs-type structure where H atoms occupy the tetrahedral [Nd(4)] site. The hydrogenation induces an increase in the unit cell volume close to 6%. The investigation of NdCoSiH by magnetization measurements reveals its ferromagnetic behavior below T(C) = 20.5(5) K. Neutron powder diffraction shows that the T(C) temperature is associated with a ferromagnetic arrangement of the Nd moments (2.3(2) mu(B) at 1.5 K) parallel to the c axis as observed for NdFeSi. The magnetic properties, magnetic structure, and the value of the Nd ordered magnetic moment evidenced for NdCoSiH are discussed using both band structure calculations and a comparison with the behavior of NdCoSi and NdFeSi.

Synthesis and characterization of the crystal structure and magnetic properties of the ternary manganese vanadate NaMnVO4.

A new ternary manganese vanadate, NaMnVO(4), was synthesized by solid state reaction route, and its crystal structure and magnetic properties were characterized by X-ray diffraction, magnetic susceptibility and specific heat measurements, and by density functional calculations. NaMnVO(4) crystallizes in the maricite-type structure with space group Pnma, a = 9.563(1) A, b = 6.882(1) A, c = 5.316(1) A, and Z = 4. NaMnVO(4) contains MnO(4) chains made up of edge-sharing MnO(6) octahedra, and these chains are interlinked by VO(4) tetrahedra. The magnetic susceptibility has a broad maximum at T(max) = 24 K and follows the Curie-Weiss behavior above 70 K with θ = -62 K. NaMnVO(4) undergoes a three-dimensional antiferromagnetic ordering at T(N) = 11.8 K. The spin exchanges of NaMnVO(4) are dominated by the intrachain antiferromagnetic exchange, and the interchain spin exchanges are spin-frustrated. The most probable magnetic structure of the ordered magnetic state below T(N) was predicted on the basis of the extracted spin exchanges.

Investigation of the new P'3-Na0.60VO2 phase: structural and physical properties.

A new layered phase Na(0.60)VO(2) was synthesized by chemical deintercalation of sodium from the pristine compound O3-NaVO(2). The Na(0.60)VO(2) compound exhibits a distorted P'3-type oxygen stacking (AABBCC) with an average monoclinic unit cell containing a = 4.9862(14) A, b = 2.8708(8) A, c = 5.917(2) A, and beta = 104.36(3) degrees. A modulated structure was observed by transmission electron microscopy and X-ray diffraction (XRD) measurements. Indexation of the XRD pattern was achieved by using the q vector equal to 0.44b*, and the 4D superspace group C2/m (0 beta 0) s0 was then deduced. The specific heat measurement showed a strong correlated system with a gamma value of around 20 mJ x mol(-1) x K(-2). The electrical conductivity shows a semiconductor-like behavior with an activation energy of 0.52 eV. A paramagnetic behavior of the susceptibility is observed below room temperature with a Curie constant equal to C = 0.076 emu x K(-1) x mol(-1) x Oe(-1). To explain this small value, a model of pseudotriangular clusters of vanadium with a random distribution of V(3+) and V(4+) was considered.

On the strongly correlated electron hydride Ce2Ni2MgH7.7.

The intermediate valence compound Ce 2Ni 2Mg absorbs irreversibly hydrogen when exposed under 1 MPa of H 2 pressure at room temperature. The resulting hydride Ce 2Ni 2MgH 7.7 is stable in air and crystallizes as the deuteride La 2Ni 2MgD 8 in a monoclinic structure (space group P2 1 /c) with the unit cell parameters a = 11.7620(2), b = 7.7687(2), and c = 11.8969(2) A and beta = 92.75 degrees . The H-insertion in Ce 2Ni 2Mg induces a structural transition from a tetragonal to a monoclinic symmetry with an unit cell volume expansion Delta V m/ V m approximately 24.9%. The investigation of the hydride by magnetization, electrical resistivity, and specific heat measurements indicates a change from an intermediate valence behavior to a non-magnetic strongly correlated electron system. This transition results from a change of the coupling constant J cf between 4f(Ce) and conduction electrons induced by the hydrogenation.

Oxygen vacancy ordering in SrFe0.25Co0.75O2.63 perovskite material.

SrFe0.25Co0.75O2.63 was synthesized by a solid-state reaction. Its structural study at room temperature using conventional X-ray as well as neutron powder diffraction, electron diffraction and high-resolution transmission electron microscopy is presented. An oxygen-vacancy ordering related to the "314" model known for the Sr3Y1Co4O10.5 oxide is proposed despite neither an A-site ordering nor an A-site mismatch. By means of Mössbauer spectroscopy, Mohr salt titration and the difference in the neutron cross sections of Fe and Co, a cation distribution within the crystallographic sites as the following Sr4(Fe0.143+Co0.363+)48h(Fe0.114+Co0.144+Co0.253+)48fO10.52 is suggested, highlighting a natural layered structure with Fe and Co in higher oxidation states in the oxygen replete layers than in the oxygen deficient ones.

Comparison of the crystal structures and magnetic properties of the low- and high-temperature forms of AgCuPO4: crystal structure determination, magnetic susceptibility measurements, and spin dimer analysis.

The crystal structure of the low-temperature form of AgCuPO4 (i.e., alpha-AgCuPO4) was determined by powder X-ray diffraction and was compared with that of the high-temperature form of AgCuPO4 (i.e., beta-AgCuPO4). The magnetic properties of the two forms were examined by measuring their magnetic susceptibilities and evaluating the relative strengths of their spin-exchange interactions on the basis of spin-dimer analysis. Both forms of AgCuPO4 have layers of Cu2P2O8 alternating with silver-atom double layers; beta-AgCuPO4 has two Cu2P2O8 layers per unit cell, while alpha-AgCuPO4 has one. The coordinate environment of each Cu2+ ion is close to being a distorted square pyramid in alpha-AgCuPO4, but it is close to being a distorted trigonal bipyramid in beta-AgCuPO4. The magnetic susceptibilities of alpha- and beta-AgCuPO4 are well simulated by an antiferromagnetic alternating-chain model, which leads to J/k(B) = -146.1 K and alphaJ/k(B) = -75.8 K for alpha-AgCuPO4, and J/k(B) = -82.6 K and alphaJ/k(B) = -31.7 K for beta-AgCuPO4 (with the convention in which the spin-exchange parameter between two adjacent spin sites is written as 2J). The spin gaps, delta/k(B), obtained from these parameters are 93.7 K for alpha-AgCuPO4 and 62.3 K for beta-AgCuPO4. The strongest spin exchange in both forms of AgCuPO4 comes from a super-superexchange path, and this interaction is stronger for alpha-AgCuPO4 than for beta-AgCuPO4 by a factor of approximately 2, in good agreement with the experiment. Our analysis supports the use of this model for beta-AgCuPO4 and indicates that the spin lattice of alpha-AgCuPO4 would be better described by a two-dimensional net made up of weakly interacting alternating chains.

Sodium calcium orthovanadate, NaCa4(VO4)3.

Single crystals of sodium tetracalcium trivanadium dodecaoxide were prepared by melting a powder sample of NaCa4(VO4)3 at 1673 K, followed by slow cooling to room temperature. The compound crystallizes in the Pnma space group and is isostructural with the mineral silicocarnotite, Ca5(PO4)2SiO4. The structure is composed of isolated VO4 tetrahedra linked by sodium and calcium cations disordered over eight- and seven-coordinated sites.

Synthesis, crystal structure, magnetic properties, and electronic structure of the new ternary vanadate CuMnVO4.

A new magnetic oxide, CuMnVO4, was prepared, and its crystal structure was determined by single-crystal X-ray diffraction. The magnetic properties of CuMnVO4 were characterized by magnetic susceptibility and specific heat measurements, and the spin exchange interactions of CuMnVO4 were analyzed on the basis of spin-polarized electronic band structure calculations. CuMnVO4 contains MnO4 chains made up of edge-sharing MnO6 octahedra containing high-spin Mn2+ cations. Our work shows that CuMnVO4 undergoes a three-dimensional antiferromagnetic transition at approximately 20 K. Both the intrachain and interchain spin exchanges are antiferromagnetic, and the interchain spin exchange is not negligible compared to the intrachain spin exchange.

Tetrastrontium dimanganese copper nonaoxide, Sr4Mn2CuO9.

Single crystals of Sr(4)Mn(2.09)Cu(0.91)O(9) have been grown by flux synthesis and the structure, closely related to the hexagonal perovskite 2H, was solved from single-crystal X-ray data in space group P321. The structure of Sr(4)Mn(2)CuO(9) is composed of chains of face-sharing polyhedra with a sequence of two octahedra and one trigonal prism. The octahedra are filled by Mn atoms and the Cu atoms are randomly distributed at the centres of the square faces of the trigonal prism. A stacking fault is observed within one of the two chains, which can be attributed to a shifting of the chain along the c axis.